Sulfochlorohydrocarbons and method for making them



jph ompositions of the halo ens combined practice of our invention constitute the sulfohyactivation, for example, with steam, sulfur, carbon dioxide, and the like. 20 g g g g ggg The compositions of this invention are chemical combinations of carbon, sulfur, hydrogen and Per Cent Per Cent halogen. They are hard, black, insoluble, in- Carbon 47.70 7H3 fusible, dense, generally non-pourous, and are and those in group 2 are termed chlorosulfocar- Table I.

TABLE I responding iodine, bromine and fluorine compounds may be used. Their use, however, is Gmu 2 limited by the temperature at which competing H I P 50 reactions occur involving the loss of carbon as Per Cm Per Cent volatile products; the maximum temperature for carbon 5H5 Q usefulness is about 1100 F. or less when using Hy rogen 3 l l0.l or less such agentg ,Sulfurv 25-15 -5 em rine -15 V 15.15 Atmospheric pressure usually suflices for the 0015031) M halogenating reaction, although pressures some- What greater may be employed to reduce the Includes any oxy n and/or nitrogen in chemitime; of treatment or to lower somewhat the Patented Jan. 23, 1951 v SULFOCHLOROHYDROCARBONS AND METHOD FOR MAKING THEM Bernard W. 'Gamson and Robert H. Elkins, Chicago, 111., assignors to Great Lakes Carbon Corporation, Morton Grove, 111., a corporation of Delaware No Drawing. Application May 25, 1948, Serial No. 29,197

13 Claims. (01. 260-139) Our invention relates to solid infusible, amor- The raw materials which are chlorinated in the with carbon, hydrogen and sulfur and to the drocarbons and the sulfocarbons which are demode of preparation thereof. scribed in the co-pending application of Bernard An object of this invention is to produce sub- 6 W. Gamson, Ser. No. 649,730, filed February '23, stances in which the carbon exists in a reactive 1946, now U. S. PatentNo. 2,447,004, issued August form in chemical combination with hydrogen, 17, 1948. halogen and sulfur and is suitable for the syn- The sulfocarbons are produced by reacting sulthesis of carbon tetrafiuoride and other fluoro fur with specific lique'fiable hydrocarbons at a carbons. 10 temperature of about 450 to about 625 F. to form Anotherobject is to produce solid amorphous a solid infusible mass. The sulfocarbons result reactive compounding agents useful in finely diwhen the sulfohydrocarbons are calcined at a vided form in natural and synthetic rubber fOrmtemperature of 1100 F. to 1-800 F. Both types ulations, plastic or resinous compositions, espeof the products are greyish to black infusible cially in the chlorinated varieties, as an aid to 5 solids which have chemical compositions in the thevulcanization and reinforcement thereof. percentage ranges shown for each in Table II.

Still another object is the use of these sub- TABLE II stances in the preparation of solid adsorbents by 50-25 25-6 amorphous. The range of composition is as fol- Negligible to .5

lows:

e c The halogenation of the sulfohydrocarbon to Carbon 50-90 produce the compositions of the present inven- Hydrogen 3- 0.1 tion is accomplished, preferably by the direct ac- Halogen 25-- L5 tion of substantially pure gaseous halogen, such Sulfur 25- 5.0 as chlorine, bromine, iodine or fluorine, at a temperature within the range of 100 F. to 1100 F. For the best results the temperatures are in the range of about 300 F. to about 1000 F. Generally, thesulfohydrocarbons are the more easily halogenated at the lower temperatures than the sulfocarbons. The choice of temperature is dependent upon the degree of halogenation desired as well as the character desired of the finished product.

The sulfocarbons are generally halogenated at a temperature in the rangeof 300 to about 1800 F. and usually not above 1500 F.

Other chlorinating agents may be used in place of chlorine, such as the sulfur chlorides, thionyl chloride, nitrosyl chloride and the like. The cor- In addition there may be incidental proportions of ash, as well as very low percentages of oxygen and nitrogen, probably in combined form. The real density may vary from about 1.4 to 1.9. 35

The compositions of this invention may further be classified into twogroups for the purpose of characterizing and defining them, and to indicate ina general way their relationship to the raw materials from which they are derived. Those in group 1 are termed chlorosulfohydrocarbon,

bon. These substances are greyish to black infusible solids which have chemical compositions in the percentage rangesshown for each group in ical combination. temperature otherwise required.

The course of the chlorination reaction involves both dehydrogenation and desuifurization, each depending to a degree on the starting material and temperature employed. The volatile products comprise hydrogen chloride, sulfur chlorides predominantly sulfur monochloride and some unreacted chlorine. There issubstantially no loss of carbon in the presence of chlorine to form volatile products at temperatures below about 1200 F. It is apparent, of course, thatuseful by-products may be recovered from the gaseous eiiiuent and that unreacted chlorine may be separated and recycled.

The above remarks on the course of the chlorination reaction apply more particularly to the treatment of the sulfocarbons. In the case of the sulfo-hydrocarbons, the chlorination thereof above their temperatures of initial formation ,(625 F. or less) is accompanied to some extent by a thermal reaction evolving hydrogen sulfide for the most part. Such hydrogen sulfide is further reactive with the chlorine to form hydrogen chloride and sulfur monoch oride but such reaction products have not been observed to be detrimental to the solid chlorinated product since the gaseous products are swept out of the reaction zone by the incoming chlorine feed almost immediately after formation.

The chlorosulfohydrocarbons of the group 1 classification usually result from the chlorination of sulfohvdrocarbons at temperatures up to,

say, about 800 F. The chlorosulfocarbons of:

the Group 2 classification, on the other hand, may be produced in at least two different ways. First. by chlorinating a sulfocarbon at any temperature selected in the preferred range of 300' F. to 1500 F. Second, by chlorinating a sulfo-.

hydrocarbon above its temperature of initial formation (up to 625 F), preferably at about 700 F. to 1500 F. To form the sulfochlorocarbons or their corresponding halogen counterparts in the second manner described, the operation should either take place at 1100 F. or above, or, if below 1100 F., be fol owed by a heating step at a higher temperature in the indicated range.

Heat-soaking for several hours of the various chlorinated products at the temperature of The com ositions of Group 1 are further distinguished from tho-"e of group 2 in that they tend to be unstable at the temperatures of formation of the latter say, above about 900 F. This instability is indicated by the evolution of part of the chlorine at the ele ated temperatures.

A specific example of this invention consists in placing a 6-10 mesh'(Tvler Standard Screen) granular packed bed of the solid charge within a one to three inch diameter heated tube maintainable at a constant temperature by an external heating furnace. purging with nitrogen. and then passing chlorine or ot er halogen gas through the bed at substantially atmospheric pressure at the desired temperature. When the degree of ch orination desired has been obtained, the flow of chlorine is stopped and the bed is purged with nitrogen, cooled and discharged.

Prior to cooling anddischarging, the product may be heat-soaked at the temperature of ionmationor a higher temperature for a further period of time, depending on the composition of the end-product desired.

As an alternative embodiment, a more finely crushed charge may be treated with chlorine in a suitable system wherein the gaseous halogen as well as the gaseous or vaporized reaction products maintains the solid particles in an ebulient state generally referred to as fluidized. Heatsoaking at the temperature of chlorination to somewhat higher temperatures may be conducted by replacing the chlorine or other halogen with an unreactive flowing gas such as nitrogen.

Having now defined and described the compositions characterized as chlorosulfohydrocarcons and chlorosulfocarbons and the manner by which they may be produced, examples are given below to illustrate more fully the nature of our invention, but not to limit the invention to the exact embodiments shown.

EXADELE I The chZorosulfohydrocarbons Sulfohydrocarbons were produced by forming a uniform mixture of a petroleum pitch (8.5% combined hydrogen) with an amount of sulfur stoichiometrically equivalent to its hydrogen content. The mixture was heated to 625 F. and the resulting solid crushed to 6-10 mesh to form a solid infusible amorphous mass of the compositio shown in Table III. Gaseous chlorine was passed over granules of the sulfo-hydrocarbons thus formed under various indicated conditions at atmospheric pressure. The charge was contained in a silica tube heated by an electric furnace, the bed purged with nitrogen. It was heated to temperature, and chlorine passed therethrough to the desired degree of reaction, then purged with nitrogen, cooled to room temperature, and the product discharged. Table III shows the composition of the raw materials. Table IV shows the various conditions for the chlorination of each sample of raw material and the composition of the product which resulted. Analyses are given calculated to an ash-free basis. In these runs substantially all of the carbon was recovered in the product. The resulting products are examples of the chlorosulfohydrocarbon compositions.

TABLE III Composition of the sulfohydrocavbon raw materials Run No. 1 2 3 Per cent Par (mt Per cent 1 Numbers correspond to the run numbers given in Table IV.

TABLE IV Chlorination conditions and products Nora-Run 1 made on a 400 gram charge in a 3 inch diameter tube. Runs 2 and 3 made on a 50 gram chargem a 1 inch diameter tube,

5 mam n The chlorosulfocwroons 1.$ulfocarbons which .had been produced by the calcination at 1100-1800" F.,-iof;a sulfohydroear- 'bon..made as "described above were treated :with

{Table VI shows the conditions for .chlorinating eachand the composition of theresulting prod- .ucts. These products, containing "substantially all of the carbon from the raw materials"; are examples of the chlorosulfocarbon compositions.

Analyses-are given on an-ash-free'basis1 TABLE V 1 Q Lo mposition of suljocarb'on rawme'terials Run'NoJ 4 5 a Per cent Carbon. Hydrogen- Run Nos. correspond to those in Table VI.

Chlorination conditions and products Chlorination Product, per composition a I I p o Temp. Ft. 301: Time, Car- Bull 7 Chlo- F. I per hr. Hours, boni Hydrogen fur rinc Nora-Runs 5a and b made on a 400 gram harge in a 3 inch diameter tube. Runs 4 and 6 made on a 50 gram'charge in a 1 inch diameter tube.

EXAMPLE III Calcining a chlorosulfohydrocarbon TABLE VII chlorosulfohydrocarbon baht??? L ll From chlori- Calcined hydrocarbon nation at V hr. at

Per cent Per cent Per cent 2. 7 i 1. 6 72 Sulfur 43. r 34. 6 13. 7 (hlnrina I 10. 6 O

The chlorinated product contained all of the carbon present in the raw material and after its calcination approximately 97.5 of the carbon remained in the chlorine-free product. The composition is more reactive to produce carbon'di- 6 sulfide by treatment with sulfur vapor at 1200- 1800" It, than the parent'material. vIt exhibits absorptive'properties'which is increasedlbyztreating with "steam rat 1000-1600" F.

Sulfurmonoc'hloride as "thechlorinating agent A'sulfocarbon which had been prepared at a 'calcination-temperature of =1400 F. was "crushed to 6-10 mesh granules and grams were charged into a one-inch diameter silica tubefurnace at 1400" F. 'to 'form'a packed bed. After purging with nitrogen sulfurmonochloride was drippedslowly through the charge for two hours; theoutletwas at atmospheric pressure. A chlorosulfocarbon product was obtained. Analyses ash-free basis) of the raw material and chlorinated .product therefrom are shown in Table VIII.

TABLE VIII Raw Ma- Chlorosulioterial carbon Per cent Per cent Carbon 89. 0 76. 6 1. 0 0. 1 '10. 0' 10.0 0 12. 4

The chlorosulfocarbon'products of runsfizrand bin Example 11 were subjected :to X-ray diffraction analyses which confirmed substantially the state of chemical union between the elements of the .composition.

In the diffraction pattern for the chlorosulfocarbon prepared at 1400 F. (5b), faint diffuse rings were observed for a graphite structure at 3.8 and 2.1 Angstroms. Another diffuse ring was found at 10 Angstroms for combined sulfur; crystalline. sulfur was absent. Traces of several lines characteristics for compounds of chlorine were observed.

The difiraction pattern for the chlorosulfocarbon prepared at 300 F. (run 5a) showed an identical pattern, except that the graphite structure was less marked.

In either case, however, the samples were found to be highly amorphous.

EXAMPLE V When substituting bromine, iodine or fluorine for the chlorine used in examples, compositions containing 50-65% carbon; 15-22% sulfur; 1-2% hydrogen and 16-21% halogen are obtained.

EXAIVLPLE VI In a like manner, substitution of bromine, iodine or fluorine for chlorine in runs as in Example II, the carbon content of the resulting compositions is 70-90%; hydrogen 0.5 to 1%; sulfur 5-15%; and halogen 212%.

The compositions of Examples V and VI are convertible to the corresponding carbon tetra halides.

By passing mixed sulfur and chlorine vapors over the compositions above described, sulfur monochloride, carbon tetrachloride and carbon disulfide are obtained. Temperatures used are 1100-1800 F. preferably, 1200-1600 F. The carbon is eventually completely consumed. Similar effects are obtained with the other halogen compounds.

We claim as our invention:

1. A process which comprises heating an amor- 7 phous solid iniuslble insoluble sultohydrocarbon ously passing a halogen over the compound thereby forming a solid infusible insoluble amorphous composition of carbon, hydrogen, sulfur, halogen and hydrogen in chemical combination.

3. A process which comprises heating an amorphous solid infusible insoluble sulfocarbon to a temperature ofabout 300-1500 F. and continuously passing a halogen over the compound thereby forming a solid infusible insoluble amorphous composition of carbon, hydrogen, sulfur and halogen in chemical combination.

4. A solid, dense, infusible, insoluble, amorphous composition consisting of carbon 50-90%; hydrogen 0.1-3%; sulfur 5-25%; and halogen l.5 all in chemical combination.

5. The composition of claim 4 wherein the halogen is chlorine.

'6. The composition of claim 4 wherein the halogen is bromine.

7. A solid, dense, infusible, insoluble, amorphous composition consisting of carbon -65%; hydrogen 1-3% sulfur, 15-25%; and halogen '15-25% all in chemical combination. l 1 f 8. The composition of claim 7 wherein the halogen is chlorine. V

9. A solid, dense, infusible, insoluble, amorphous'composition consisting of carbon -90%; hydrogen (ll-1.0%; chlorine 5-15% and halogen 1.5% to 15% all in chemical combination. l

10. The composition of claim 9 wherein the halogen is chlorine.

11. A composition comprising a dense, infusible, insoluble, amorphous solid consisting of carbon 50-90%; hydrogen 0.1-3%; sulfur 525%;

and halogen 1 .5-25%, all in chemical combination.

""12. The composition of claim 11 wherein the I; halogen is'chlorine.

1 13. A process which comprises'heating a solid, infusible, insoluble amorphous composition consisting essentially of:

. Per cent 10 Carbon 47-93 Hydrogen 4-0.3 Sulfur 50-6 all in chemical combination, with-chlorine at a temperature of -1800" F. to produce an infusible, insoluble amorphous solid having the cornposition: r

Per cent all in chemical combination.

. BERNARD W. GAMSON.

' ROBERT H. ELKINS.

REFERENCES CITED The following references are of record in the file of this patent:

Great Britain of 1937 

1. A PROCESS WHICH COMPRISES HEATING AN AMORPHOUS SOLID INFUSIBLE INSOLUBLE SULFOHYDROCARBON TO A TEMPERATURE OF ABOUT 100-1100* F. AND CONTINUOUSLY PASSING A HALOGEN OVER THE COMPOUND THEREBY FORMING A SOLID INFUSIBLE INSOLUBLE AMORPHOUS COMPOSITION OF CARBON, HYDROGEN, SULPHUR AND HALOGEN IN CHEMICAL COMBINATION. 